Novel multifunctional hydroxy compounds and methods for the preparation thereof

ABSTRACT

N-alkylated derivatives of 2-amino-2-hydrocarbylthiomethyl-11,3-propanediols, useful as flotation agents, rubber modifiers, and chelating agents in the separation of metals, are produced by reacting 2-amino-2-hydrocarbylthiomethyl-1,3-propanediols with organic halides. Thiols can be produced by reacting arylmethylated or alkarylmethylated derivatives of the above compounds with an alkali metal in the presence of ammonia.

United States Patent Clarence R. Bresson; Raymond L. Cobb, both 01 c/oPhillips Petroleum Company, Bartlesville, Okla. 21 Appl. No. 749,990[22] Filed Aug. 5, 1968 Division' EfSEr. Nb. 492,892, Oct. 4, 1965, Pat.No. 3,414,617 [45] Patented 2S, 1971 [72] Inventors [54] NOVELMULTIFUNCTIONAL HYDROXY COMPOUNDS AND METHODS FOR THE PREPARATIONTHEREOF 4 Claims, No Drawings 260/557 R, 260/559 A, 260/559 T, 260/570.5CA,

260/570.5 R, 260/570.5 S, 260/570.8 R, 260/584 [51] Int. Cl C07c 103/00Primary Examiner-James 0. Thomas, Jr. Assistant Examiner-Ethel G. LoveAttorneyY0ung and Quigg ABSTRACT: N-alkylated derivatives of2-amino-2-hydrocarbylthiomethyl-l-l,3-propanediols. useful as flotationagents, rubber modifiers, and chelating agents in the separation ofmetals, are produced by reactingZ-amino-Z-hydrocarbylthiomethyl-l,3-propanediols with organic halides.Thiols can be produced by reacting arylmethylated or alkarylmethylatedderivatives of the above compounds with an alkali metal in the presenceof ammonia.

NOVEL MULTIFUNCTIONAL HYDROXY COMPOUNDS AND METHODS FOR THE PREPARATIONTHEREOF This is a divisional application of Application Ser. No.

492,892, filed Oct. 4, 1965, now issued as US. Pat. No. 3,414,617granted Dec. 3, 1968.

In one aspect this invention relates to novel hydrocarbylthiomethyl andmercaptomethyl-substituted propandediols. In another aspect thisinvention relates to N-alkylated derivatives of2-amino-Z-hydrocarbylthiomethyl-l -l,, 3- propanediols. In still anotheraspect this invention relates to a method for preparing such novelcompounds.

In accordance with this invention, an N-alkylated derivative of a2-amino-2-hydrocarbylthiomethyl-1-1 ,3-propanediol having the formula isproduced by the reaction of a 2-amino-2hydrocarbylthiomethyl-l l,3-propanediol having the formula with an organic halide having theformula RX whereby R" replaces one of the hydrogens on the amino groupwith the liberation of HX.

With reference to the above formulas R is at least one member selectedfrom the group consisting of hydrogen and alkyl containing one to threecarbon atoms; R is a monovalent hydrocarbyl radical selected from thegroup 6011' sisting of alkyl, cycloalkyl, aryl, and combinations thereofsuch as alkaryl, aralkyl, and the like, said monovalent hydrocarbylradical containing one to 12 carbon atoms; R is a member selected fromthe group consisting of unsubstituted and substituted alkyl, cycloalkyl,and aralkyl radicals, and combinations thereof such as alkylcycloalkyl,alkylaralkyl, and the like, containing one to 12 carbon atoms, thesubstituent in the substituted radicals being a monovalent radical suchas hydroxy, hydrocarbyloxy, hydrocarbylthio, carboxy, carbamoyl, and thelike; and X is a halogen selected from the group consisting of chlorine,bromine, and iodine, preferably chlorine or bromine; and wherein thenumber of carbon atoms in formula I is within the range of six to 36.

Examples of novel products made according to the process describedhereinabove are as follows:

2-methylamino-2-methylthiomethyll ,3-p ropanediol2-ethylamino-2-[l-(isopropylthio)butyl]-1,3-propanediol2-isopropylamino2-[1-(ethylthio)ethyl]-l,3-propanediol2-tertbutylamino-2-[ 1-( sec-butylthio)- l -methylpropyl]-1,3-propanediol Z-hexylamino-2-tertbutylthiomethyl l ,3-butanediol 3-(1,2-diethylpentylamino )-3-hyxylthiomethyl-2,4-hexanediol2-dodecylamino-2-( 3-methyloctyl )thiomethyll ,S-hex' anediol-dodecylamino-5-[ l-(dodeeylthio)propyl]-4,6-nonanediol2-cyelohexylamino-2decylthiomethyll ,3-propanediol2(2-methylcyclopentylamino)-2-cyclohexylthiomethyl-4-methyl-1,3pentanediol 2-( 2-eyclohexylethylamino)-b propanediol 2-(Z-phenylethylamino )-2-p-tolylthiomethyll ,3-

propanediol 2-(4-methylbenzylamino)-2-[l-(propylthio)-2-methylpropyl]-1,3-propanediol 5-(3'hydroxypropylamino)-5-[ l-(dodecylthio)propyl]-4,6

nonanediol 2-(4-ethoxybutylamino)-2-methylthiomethyld'methyl-l ,3-

butanediol 2-( 3-methylthiopropylamino )-2'propylthiomethyll ,3-

Z-phenylthiomethyll ,3-

propanediol 2-( 3-earboxycyclopentylamino )-2-butylthiomethyll ,3-

propanediol 2-( B-carbamoylpropyl amino )-2-phenylthiomethyll ,3-

propanediol 2-methylamino-2-benzylthiomethyll ,3-butanediol Examples ofcompounds of formula II suitable for reacting with an organic halide arethe following:

2-amino-2-methylthiomethyl-l ,3-propanediol 2-amino-2-[l-(ethylthio)ethyl ]-l ,3-propanediol 2-amino-2-[ l-(isopropylthio)butyl l ,3-propanediol 2-amino-2-[l-(sec-butylthio)-l-methylpropyl1 ,3-

propanediol Z-amino-Ltert-butylthiomethyl-l ,3-butanediol3-amino-3-hexylthiomethyl-2,4-hexanediol 2-amino-2-(3-methyloctyl)thiomethyl-l ,3-hexanediol 2-amino-2-decylthiomethyll,3-propanediol 2-amino-2-eyclohexylthiomethyl-4-methyll ,3-pentanediol2-amino-2-phenylthiomethyl-l ,3'propanediol 2-amino-2-p-tolylthiomethyll,3-propanediol 2-amino-2-[ l-(propylthio l-Z-methylpropyl l ,3-

propanediol 5-amino-5-[ l-(dodecylthio)propyl ]-4,6-nonanediol2-amino-2methylthiomethyl-3-methyll ,3-butanediol2-amino-2-benzylthiomethyl-l ,3-butanediol Examples of organic halidecompounds suitable in the process of this invention are the following:

bromomethane iodoethane 2chloropropane 2-bromo-2-methylpropanel-chlorohexane 3-bromo4-ethylheptane l-chlorododecane chlorocyclohexane1-bromo-2-methylcyclopentane l-iodo-2-eyclohexylethanel-chloro-2-phenylethane a-bromo-pxylene 3bromopropanoll-chloro-4-ethoxybutane l-bromo3-methylthiopropanel-chloro-3-carboxycyclopentane 3-bromobutyramide ln carrying out theprocess ofthis invention, the mol ratio ofZ-amino-Z-hydrocarbylthiomethyll ,3-propanediol to organic halide ispreferably about 1/1; however, it is within the scope of the inventionthat mol ratios ranging from 0.5/1 to 2/1 can be employed. The aminecompound can be employed as the free base which can be obtained from asalt thereof, e.g. as a hydrohalide or sulfate; thus, if the amine isavailable as the salt, it is preferably first treated with a base toliberate the free amine.

Although the reaction temperature can vary over a wide range, it wouldgenerally be within the range of about O250 C., preferably within therange of about 50-l 50 C. The desired reaction time also varies over awide range, depending in part on the reaction temperature and the natureof the reactants, but will generally be within the range of about 10minutes to about 5 days, preferably within the range of from 5 hours to3 days.

In the operation of the process of this invention a solvent is notrequired; however, in the preferred embodiment solvents are employed.Examples of some suitable solvents include alcohols such as methanol,ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, n-hexylalcohol; alcohol; such as ethyl ether, n-propyl ether, n-butyl ether.tetrahydrofuran, dioxane, dimethyl ether of ethylene glycol; and amidessuch as dimethylformamide, dimethylacetamide, and N-methylpyr rolidone.

The pressure of the reaction is preferably autogenous and need be onlysufficient to maintain the reactants and their solvents substantially ina liquid phase.

As a further aspect of this invention, when R is arylmethyl oralkarylmethyl, the said N-alkylated derivative having the formula CRZOHR'SCR CNHR CRgOH is cleaved by treatment with an alkali metal selectedfrom the group consisting of lithium, sodium, potassium rubidium, andcesium in the presence of ammonia to give a thiol having the formula(III) wherein R and R" are as defined hereinabove. It is noted that whenR" contains an arylmethyl group or an alkarylmethyl group attached to asulfide linkage, these hydrocarbyl groups will be cleaved by an alkalimetal and replaced with hydrogen.

Examples of compounds of formula lll ARE AS FOL- LOWS:

2-(4-ethoxybutylamino )-2-mercaptomethyl-3-methyl-l ,3-

butanediol 2-(3-methylthiopropylamino)-2-mercaptomethyl-1,3-

propanediol 2-( 3-carboxycyclopentylamino )-2-mercaptomethyl-l ,3-

propanediol 2-(3-carbamoylpropylamino)-2-mercaptomethyl-1,3-

propanediol In this cleavage step, the amount of alkali metal actuallyrequired will vary depending upon the number of reactive groups such ashydroxy, carboxy, arylmethylthio, and alkarylmethylthio which arepresent, approximately lmol of alkali metal being required for eachgroup such as hydroxy or carboxy containing a hydrogen atom readilyreplaceable by the alkali metal and approximately 1.8 mols of alkalimetal being required for each arylmethylthio or alkarylmethylthio group.This amount of alkali metal is usually sufficient to impart a blue castto the resulting solution which persists for at least 30 minutes. Atleast 3 mols, preferably at least 10 mols, of ammonia per mol of alkalimetal is employed. The amine containing the arylmethylthio oralkarylmethylthio group can be employed as the free base or as a salt,e.g., hydrohalide or sulfate thereof. Although the reaction temperaturein this cleavage step can vary over a wide range, it will generally bewithin the range of about lO0 to 50 C., usually being approximately thenormal boiling point of liquid ammonia. The desired reaction time variesover a wide range, depending in part on the reaction temperature, butwill generally be within the range of about 30 minutes to about 12hours, usually being within the range of from 1 to 6 hours. Although theammonia conveniently serves as a solvent, an additional solvent can beused in conjunction with the ammonia if desired.

Examples of suitable additional solvents include ethers such as ethylether, n-propyl ether, n-butyl ether, tetrahydrofuran, dioxane, dimethylether of ethylene glycol and the like. Less preferably alcohols such asmethanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,n-hexyl alcohol and the like can be employed.

The novel compounds produced by the process of this invention are usefulas flotation agents, and those compounds which are cleaved to form themercapto substituents are useful as intermediates in the preparation ofantiradiation drugs. These compounds are also useful as rubber modifiersand as chelating agents in the separation of metals.

It is to be understood that these compounds can be prepared in'acontinuous medium in the manner disclosed hereinabove and can berecovered by conventional methods, such as crystallization,distillation, solvent extraction, and the like. These recoveryoperations are conventional steps and are familiar to those skilled inthe art. The technique for the recovery of specific compounds can varysomewhat due to differences in molecular weight, solubility, boilingpoint, and the like.

The following examples are presented merely for descriptive purposes andthe invention is not to be unduly limited thereby.

EXAMPLEI Preparation of 2-benzylthiomethyl-2-( n-octylamino)-l ,3-propanediol Hydrochloride A solution of 131.9 g. (0.5 mol) of 2-amino-2-benzylthiomethyl-l,3-propanediol hydrochloride in 500 ml. of ethanol wasneutralized with 20 g. (0.5 mol) of sodium hydroxide, and the sodiumchloride was removed by filtration. The filtrate was heated at refluxtemperature with 74.3 g. (0.5 mol) of n-octyl chloride for 24 hours. Thesolution was distilled through a 45-in. Vigreux column until the pottemperature reached C., at which point an exothermic reaction occurredand the temperature rose to 155 C. After 1 hour, the temperature beganto fall, and the reaction mixture was held at C. for an additional hourwith external heating. Unreacted n-octyl chloride (0.124 mol) wasremoved by distillation. The residual oil was dissolved in 500 m1. oftoluene, and the solution was saturated with hydrogen chloride. Theresulting semisolid was trituratcd with warm chloroform to give a 20percent yield (38.5 g.) of the dried product,2-benzylthiomethyl-2-(n-octylamino)-n1,3- propanediol hydrochloride,m.p. 127-l28 C. Recrystallization from tetrahydrofuran did not changethe melting point. The elemental analysis was as follows:

EXAMPLE n Preparation of 2-Mercaptomethyl-2-(n-octylamino)-1 ,3-propanediol Hydrochloride A slurry of 31 g. (0.08 mol) of2-(n-octylamino)-2- benzylthiomethyl-l,3-propanediol hydrochloride in100 ml. of tetrahydrofuran was added to a liter of liquid ammonia atapproximately 33 C. and atmospheric pressure. Addition of 7 g. (0.30mol) of sodium resulted in a solution which remained blue for an hour.The solution was neutralized with 16 g. (0.30 mol) of ammonium chloride.After addition of 250 ml. of npropyl alcohol, the ammonia was boiledoff. The mixture was then saturated with hydrogen chloride. Afterwarming, the inorganic salts were removed by filtration. The filtratewas stripped to dryness The residual oil was extracted with 250 ml. ofether. The viscous residue was dissolved in tetrahydrofuran, and thesolution was saturated with hydrogen chloride; no crystallizationoccurred. Similar attempts to induce crystallization from methanol andn-propyl alcohol as solvents were unsuccessful. The oil was dried at 100C. to give a 40 percent yield (9.0 g.) of theZ-mercaptomethyl-Z-(noctylamino)-l,3-propanediol hydrochloride. Theelemental analysis was as follows:

Preparation of 2-Benzylthiomethyl-2-(2-hydroxyethylamino)-1,3-propanediol Hydrochloride A solution of 131.9 g. (0.5 mol) of2-amino-2- benzylthiomethyll ,3-propanediol hydrochloride in 250 ml. ofmethanol was neutralized with 20 g. (0.5 mol) of sodium hydroxide. Thesodium chloride was removed by filtration. The filtrate was heated atreflux temperature for 24 hours with 40 g. (0.5 mol) of 2-chloroethanol.The solvent was removed through use of a 60 cm. column packed with glasshelices; at 120 C an exothermic reaction occurred. The dark residue wascrystallized from 250 ml. of tetrahydrofuran to give a 20 percent fluid(31 g.) of 2-benzylthiomethyl-2-(2-hydroxyethylamino-l ,3-propanediolhydrochloride, m.p. 107l08.5 C. The elemental analysis is as follows:

Preparation of 2Mercaptomethyl-2-( 2-hydroxyethylamino)- Lit-propanediolHydrochloride A slurry of 31 g. (0.1 mol) of 2-benzylthiomcthyl-2-(2-hydroxyethylamino)-l,3-propanediol hydrochloride in 150 ml. oftetrahydrofuran was added to 1 liter of liquid ammonia at approximately33 C. and atmospheric pressure. Sodium (8.5 g., 0.37 mol) was added tomaintain a blue solution for 1 hour. The solution vras neutralized with20 g. (0.37 mol) of ammonium chloride, and the ammonia was boiled off. Acold suspension of the residue in 150 ml. of n-propyl alcohol wassaturated with hydrogen chloride. The mixture was warmed, and inorganicsalts were removed by filtration. The filtrate was stripped. The residuewas washed with ether to give a crystalline solid. Tworecrystallizations from a mixture of isopropyl alcohol and methanol gavea 3] percent yield (6.8 g.) of the 2-mercaptomethyl-2-(2-hydroxyethylamino)-1,3-propanediol hydrochloride,m.p. 101.5-102 C. The elemental analysis was as follows:

Preparation of 2-Benzylthiomethyl-2-( 3-phenylpropylamino 1,3propanediolHydrochloride A solution of 66 g. (0.25 mol) of 2-amino-2-benzylthiomethyl-1,3-propanediol hydrochloride in ml. of methanol wasneutralized with 10 g. (0.25 mol) of sodium hydroxide, and the sodiumchloride was removed by filtration. The filtrate was evaporated, and thefree base was dissolved in 150 ml. of N-methylpyrrolidone. After theaddition of 39 gv (0.55 mol) of l-chloro-3-phenyl-propane. the solutionwas heated at C. for 48 hours. The reaction mixture was poured into aliter of water; the oil which separated was acidified with 50 l. ofconcentrated hydrochloric acid. Subsequent addition of water gave acrystalline solid which was recrystallized from chloroform to give a 34pcrcent yield (32 g.) of the2-benzylthiomethyl'2-(3-phenylpropyl-amino)-l .3 propanediolhydrochloride, m.pv 121 l22 C. The elemental analysis was as follows:

Preparation of 2-Mercaptomethyl-2( 3-phenylpropylamino 1,3-propanedi0lHydrochloride A slurry of 32 g. (0.08 mol) of 2-benzylthiometyl-2-(3-phenylpropyl-amino-l,3-propanediol hydrochloride in 100 ml. oftetrahydrofuran was added to 1 liter of liquid ammonia at approximately33 C. and atmospheric pressure. Sodium (8 g., 0.33 mol) was added to theresulting mixture to maintain a blue color for 1 hour. The mixture wasneutralized with 18 gv (0.34 mol) of ammonium chloride, and the ammoniawas off. A cold slurry of the residue in 200 ml. of n-propyl alcohol wassaturated with hydrogen chloride. After warming, the inorganic saltswere removed by filtration. The filtrate was stripped, and the residualoil was extracted three times with ether. Drying the residue in vacuogave 2-mercaptomethyl-2- (3-phcnylpropylamino)-l,3 -propanediolhydrochloride as a clear glass. The elemental analysis was as follows:

Element Calculated for C ,H,,N0,S HCI Found EXAMPLE VII A solution of132 g. (0.50 mol) of 2-amino-2- benzylthiomethyl-1,3-propanediolhydrochlordie in 500 ml. of tetrahydrofuran was neutralized with 20 g.(0.50 mol) of of sodium hydroxide, and the sodium chloride was removedby filtration. To the filtrate was added 53.8 g. (0.50 mol) of 3-chloro-propionamide, and the solution was heated at reflux temperaturefor 24 hours. The solvent was removed, and the reaction mixture washeated 48 hours on a steam bath. The product was dissolved in 300 ml. oftetrahydrofuran and 100 ml. of acetonitrile; cooling at l C. gave 79 g.of crude product, m.p. 119121 C. Recrystallization from tetrahydrofurangave a 27 percent yield (46 g.) of the 2-benzythiomethyl-2-(2-carbarnoylethylamino)-1,3 propanediolhydrochloride, m.p. 145147 CiThe elemental analysis was as follows:

Preparation of 2-Mercaptomethyl-2'( 2-carbamoylethylamino)-1,3-propanediol Hydrochloride A slurry of 46 g.(0.137 mol) of 2-benzylthiomethyl-2-(2-carbamoyl-ethy1amino)-1,3-propanediol hydrochloride in 200 ml. oftetrahydrofuran was added to 1 liter of liquid ammonia at approximately33 C. and atmospheric pressure; to the mixture was added 15.8 g. (0.6mol) of sodium to maintain a blue color for 1 hour. The mixture wasneutralized with 33 g. 33 g. (0.6 mol) of ammonium chloride, and theammonia was boiled off. The product was suspended in 250 ml. of coldnpropyl alcohol, and the mixture was saturated with hydrogen chloride.After arming, the inorganic salts were removed by filtration. Thefiltrate was evaporated to yield a semisolid. The latter was extractedwith 200 ml. of ether and then with 200 ml. of boiling tetrahydrofuranto remove benzyl. The waterwhite viscous oil resisted attempts atcrystallization from various solvent combinations. Portion wise additionof ether to a solution in n-propyl alcohol gave three fractions (allviscous oils) 2.9 g. 5.3 g., and 1 1.7 g., which were vacuum-dried for24 hours at 65 C. The intermediate fraction which was substantially pure2-mercapt0metyl-2-(2-carbamolethylamino)-1,3- propanediol hydrochloridewas subjected to elemental analysis. The elemental analysis was asfollows:

Gas chromatographic analysis of the sample showed the followingimpurities (in weight percent): tetrahydrofuran, 2.8; npropyl alcohol,0.2.

EXAMPLE IX Preparation of(2-Chloroethyl)cyclohexane To 100 g. (0.78 mol)of Z-cyclohexylethanol was added dropwise over a period of 30 minutes 95g. (0.8 mol) of thionyl chloride. The solution was heated on a steambath for 1 hour and then distilled through a 45-cm. Vigreux column togive an percent yield (96.7 g.) of the (2- chloroethyl)cyclohexane, b.p.l15-1l5.5 C. at 72 mm., m,

Preparation of 2-Benzylthiomethyl-l-( 1- cyclohexylethylemino)- 1,3-propanediol Hydrochloride A solution of 174 g. (0.66 mol) of 2-amino-2-benzylthiomethyl-l,3-propanediol hydrochloride in 250 ml. of methanolwas neutralized with 26.4 g. (0.66 mol) of sodium hydroxide, and thesodium chloride was removed by filtration. The solvent was stripped off.To the resulting free base was added 96 g. (0.66 mol) of (2-chloroethyl)cyclohexane in 250 ml. of tetrahydrofuran. The reaction mixture washeated at reflux temperature for 16 hours. The solvent was distilled,and the residue was heated at 140 C. for 16 hours. The crystallineproduct was recrystallized twice from 300 ml. of acetonitrile to give a36-perccnt percent yield g.) of the 2-benzylthiomethyl-1-(2-cyclohexylethylamino)-1,3- propanediolhydrochloride, m.p. l4915 1 C. The elemental analysis was as follows:

Preparation of 2-Mercaptomethyl2-(2-cyclohexylethylamino)-1,3-propanediol Hydrochloride A slurry of 90 g.(0.24 mol) of Z-benzylthiomethyLZ-(Z- cyclohexyl-ethylamino)-l,3propanediol hydrochloride in 250 ml. of tetrahydrofuran was added to 1liter of liquid ammonia at approximately C. and atmospheric pressure.The slurry was treated with 20 g. (0.87 mol) of sodium metal to maintaina blue color for 1 hour. The mixture was neutralized with 50 g. (0.93mol) of ammonium chloride, and the ammonia was evaporated. A coldmixture of the residue in 250 ml. of npropyl alcohol was saturated withhydrogen chloride. The mixture was warmed, and the inorganic salts wereremoved by filtration. The filtrate was evaporated, and the residue wasextracted twice with ether. The residue was recrystallized once from amixture of tetrahydrofuran and ether and once from a mixture ofacetonitrile and tetrahydrofuran to give a 44-percent yield (30 g.) ofthe 2-mercaptomethyl-2-(2-cyclohexylethylamino(-1,3-propanediolhydrochloride, m.p. l23135 C. The elemental analysis was as follows:

lnicrcaplanl EXAMPLE Xll Preparation of 2-Benzylthiomethyl-2-(3-hydroxypropylamino )-l ,3-propanediol Hydrochloride A solution of 113.5g. 0.5 mol) of 2-amino-2- benzylthiomethyl-l,3-propanediol, 47.3 g. (0.5mol) of 3- chloropropanol and a crystal of potassium iodide was heatedat 110 C. for 24 hours and then at 130 C. for 4 hours. Crystallizationof the product from a mixture of 200 ml. of tetrahydrofuran and 50 ml.of methanol gave a thick gel which was dispersed in 2 liters of amixture of acetonitrile and tetrahydrofuran to filter. The yield of2-benzyl-thiomethyl-2- (3-hydroxypropylamino)-l,3 -propanediolhydrochloride was 51 percent (b 83 g.), m.p. l 19-122 C. The elementalanalysis was as follows:

The elemental analysis was as follows:

Element Calculated for C H NO SHCI Found 20 C 52.24 51.1 H 7.52 7.7 N4.35 4.4 S 9.96 9.3

EXAMPLE Xlll Preparation of 2-Benzylthiomethyl-2-(2-benzylthioethylemino)-1,3-propanediol Hydrochloride A mixture of 62 g.(0.33 mol) of benzyl 2-chloroethyl sulfide, 75 g. (0.33 mol) of2-amino-2-benzylthiomethyl-1,3- propanediol, 36 g. (0.33 mol) of sodiumcarbonate, and 300 ml. of xylene was stirred vigorously under reflux for8 hours. After cooling, the mixture was diluted with an equal volume ofether and washed several times with water. The organic layer wasevaporated under aspirator pressure. The residual oil was mixed with 500ml. of isopropyl alcohol and 100 ml. of concentrated hydrochloric acid.After evaporation of the resulting solution, the residual oil wasdissolved in acetonitrile. Cooling gave the 2-benzylthiomethyl-2-( 2-benzylthioethylamino)-l,3-propanediol hydrochloride in a 65-percentyield (90 g.); recrystallization from acetonitrile gave small whitecrystals, m.p. 119 -l2l C. The elemental analysis was as follows:

benzylthioethylamino)-l,3'propanediol hydrochloride (74 g., 0.18 mol)was prepared in 1 liter ofliquid ammonia at approximately -33 C. andatmospheric pressure. Sodium (24 g., 1 mol) was added in small pieces tomaintain a blue color for 2 hours. The solution was neutralized with 20g., of ammonium chloride. All subsequent operations were carried outunder nitrogen. After eyaporation of the ammonia, 500 ml. oftetrahydrofuran and 250 m1. of 95-percent ethanol were added to theresidue. The mixture was heated to 40 C after cooling to 10 C., themixture was filtered. The solid was washed twice with isopropyl alcohol.The combined solutions were evaporated to dryness under aspiratorressure; the residual oil rapidly solidified. It was taken up in 00 ml.of hot isopropyl alcohol, and a slight turbidity was removed byfiltration. The filtrate was saturated with hydrogen chloride. Aninorganic solid separated and was removed. Evaporation and dissolutionof the residue in isopropyl alcohol gave more inorganic material, as didcooling the solution to -70 C. Finally addition of ether to the alcoholsolution gave, at -70 C., a crystalline solid that became an oil at roomtemperature. It was filtered on a funnel cooled with circulating acetonechilled at 60 C. Drying in a high vacuum overnight did not removecompletely occluded or solvated isopropyl alcohol, found upon gaschromatographic analysis. The elemental analysis was as follows:

Calculated for Element C.H NO,S,'HC1-0.8C,H,0H Found C 35.79 35 6 H 8.017 .8 N 4.97 5.1 5 22.75 21.9 (mercaptan) It is to be understood thatalthough in the preceding examples all the novel compounds werepermitted to remain as the salts thereof, that it is within the skill ofa chemist to free these novel compounds from the salt by merely treatingthem with a suitable base such as sodium or potassium hydroxide.

Obviously many modifications and variations of the present invention arepossible in the light of the above teachings. it is therefore to beunderstood that within the scope of the appending claims the inventionmay be practiced otherwise than as specifically described herein.

What is claimed is:

l. A compound selected from the group consisting of compounds having theformula wherein each R is hydrogen or an alkyl radical containing l3carbon atoms; R is an alkyl radical containing [-12 carbon atoms orhydrogen; R" is a carbamoyl substituted alkyl radical containing l-l2carbon atoms; and wherein the total number of carbon atoms in saidcompound is within the range of 636.

2. A compound selected from the group consisting of compounds having theformula CRQOH Hscmt' NHa" cmoa wherein R and R" are as defined in claim1 wherein the total number of carbon atoms in said compound is withinthe range of 636.

3. 2-Mercaptomethyl-2-(2-carbamoylethylamino)- l ,3- propanediol, theproduct of the formula of claim 2.

4. 2-(3-Carbamoyl propylaminc)Q-mercaptomethybl,3- propanediol, theproduct of the formula of claim 2.

2. A compound selected from the group consisting of compounds having theformula wherein R and R'''' are as defined in claim 1 wherein the totalnumber of carbon atoms iN said compound is within the range of 6-36. 3.2-Mercaptomethyl-2-(2-carbamoylethylamino)-1,3-propanediol, the productof the formula of claim
 2. 4. 2-(3-Carbamoylpropylamine)-2-mercaptomethyl-1,3-propanediol, the product of theformula of claim 2.